Cationic, Neutral, and Anionic Hydrides of Iridium with PSiP Pincers

Jun 2, 2017 - Starting from the five-coordinate pincer precursor [IrClH(PSiP)], this work describes synthetic routes toward hydride and polyhydride de...
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Cationic, Neutral, and Anionic Hydrides of Iridium with PSiP Pincers Elizabeth Suárez,† Pablo Plou,† Dmitry G. Gusev,‡ Marta Martín,*,† and Eduardo Sola*,† †

Instituto de Síntesis Química y Catálisis Homogénea, CSIC, Universidad de Zaragoza, Zaragoza E50009, Spain Department of Chemistry, Wilfrid Laurier University, Waterloo, Ontario N2L 3C5, Canada

‡

S Supporting Information *

ABSTRACT: This work describes synthetic routes from the known precursor [IrClH{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}] (1) to new hydride and polyhydride derivatives. Substituting the chloride ligand with triflate leads to the five-coordinate complex [IrH{κO-O3S(CF3)}{κP,P,SiSi(Me)(C6H4-2-PiPr2)2}] (2), which can undergo reversible coordination of water (H2O) or dihydrogen (H2) to generate respectively the cationic derivative [IrH{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}(OH2)2](CF3SO3) (3) or the neutral trans-hydride−dihydrogen [IrH{κO-O3S(CF3)}{κP,P,SiSi(Me)(C6H4-2-PiPr2)2}(η2-H2)] (6) in equilibrium. The use of acetonitrile or carbon monoxide (CO) excess instead of water produces stable analogues of 3 (complexes 4 or 5, respectively). The reaction between 1 and NaBH4 affords the tetrahydroborate derivative [IrH{κ2H-H2BH2}{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}] (7), which can be protonated with triflic acid to form 2 or with HBF4 to give the dinuclear cationic derivative [(μ:κ2H,κ2HBH4)[IrH{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}]2](BF4) (8). The reactions of 7 with alcohols afford either the dihydride−carbonyl [IrH2{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}(CO)] (9) or the known tetrahydride [IrH4{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}] (10), depending on the ease of alcohol decarbonylation. NMR observations and density functional theory calculations on the fluxional behavior of 10 indicate that the spatial contour of the mer PSiP framework conditions hydride-ligand exchanges. Complex 10 reacts with NaH in tetrahydrofuran to form the anionic trihydride [IrH3{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}]Na (11), which exists as a mixture of fac and mer isomers in equilibrium.

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INTRODUCTION Transition-metal hydride complexes are almost ubiquitous in organometallic catalysis and energy conversion and storage paradigms.1 In particular, those of iridium promote or mediate catalytic transformations of actual or potential industrial importance,2,3 such as hydrogenations4,5 and C−H bond functionalizations.6−9 Behind this singular reactivity are factors such as the exceptional mobility of metal-bonded hydrogen atoms,10 which enables different facile inner- and outer-sphere migrations,11,12 and their strong σ-donor character and trans influence as ligands,13 which often also determine the structures. The latter, however, become less decisive when other strong σ-donor ligands are present, as observed, for example, in hydride complexes with silyl-donor (PSiP)14 or boryl-donor (PBP) pincers.15 These ligands have emerged capable of promoting hydride complexes with distinctive structures, likely to be more reactive than conventional ones.16 Also, these strong σ-donor pincers have been observed to expedite migratory insertions into M−H bonds, thus being particularly suitable for challenging catalytic transformations such as those involving carbon dioxide.17 Aimed at extending this chemistry to compound types that can fulfill the requirements of different catalytic transformations, we describe here the preparations and structures of a variety of iridium PSiP hydrides, including dihydrogen and anionic derivatives, still unknown in the chemistry of these pincers.18 The work starts from the five-coordinate precursor [IrClH{κP,P,Si-Si(Me)© 2017 American Chemical Society

(C6H4-2-PiPr2)2}] (1), previously reported by Shimada et al.19 and, besides the new complexes, also describes in detail the dynamic behavior in solution of the known tetrahydride [IrH4{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}] (10).

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RESULTS AND DISCUSSION Just like its analogues with tBu20 and Cy21 substituents at the phosphorus and other complexes with related PSiP ligands,16 the unsaturated complex 1 displays a solid-state structure in which the empty coordination site lies trans to the silicon atom, with Cl−Ir−H and P−Ir−P angles of 159.8(12) and 163.37(3)°, respectively (see the Supporting Information). The range of possible reactions enabled by this coordination vacancy can be extended by replacing the chloride ligand with the more labile triflate: a transformation cleanly completed by 1 equiv of methyl triflate in dichloromethane (Scheme 1). The resulting complex, [IrH{κO-O3S(CF3)}{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}] (2), was found to be relatively stable and easy to handle, in contrast to the affinity for traces of adventitious water of its analogue with an aliphatic backbone at the PSiP ligand.22 This analogue was reported to readily form a κO,P,P-P(SiOH)P dihydride complex after cleavage of a water molecule and insertion of the OH fragment into the Si−Ir Received: March 30, 2017 Published: June 2, 2017 7190

DOI: 10.1021/acs.inorgchem.7b00833 Inorg. Chem. 2017, 56, 7190−7199

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Inorganic Chemistry Scheme 1

Figure 1. Structures of the neutral triflate complex 2 [Ir(1) on the left side of the image] and its cationic water adduct 3 [Ir(2)] as determined in cocrystals obtained from 2 in “wet” hexane. Ellipsoids for the anisotropic displacement parameters at the 50% level. Hydrogen atoms except hydrides, and those involved in hydrogen bonds (dotted lines) have been omitted for the sake of clarity. For bond distances and angles, see the Supporting Information.

bond. Instead of such an irreversible transformation, the treatment of 2 with water in an NMR tube in CD2Cl2 was observed to provoke just small shifts in most of the NMR signals, including the diagnostic singlets in the 31P{1H} and 19F NMR spectra, at δ +69.60 and −77.49, respectively, and the triplet corresponding to the hydride ligand in the high-field 1H NMR region, at δ −29.52 (JHP = 14.9 Hz). Decreasing the temperature provoked decoalescence of each of these shifted signals into two, whose relative intensity depended on the amount of added water. One set of signals matches those of complex 2 while the other indicates the formation of a new monohydride species, 3. The most characteristic 1H NMR signals of this new complex at 173 K are a broad triplet at δ −28.86 (JHP ≈ 16 Hz) and two equal broad resonances at δ 4.30 and 4.89, whose integrals suggest that they correspond to two nonequivalent water ligands. Consistently, the 19F NMR signal of the new species appears close to δ −79, as is expected for a free triflate anion in this solvent (see below).22 The proposed structures of 2 and its cationic water adduct [IrH{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}(OH2)2](CF3SO3) (3) were corroborated by X-ray diffraction in crystals obtained from hexane solutions of 2 treated with small amounts (microliters) of water and stored at 253 K. Remarkably, such a treatment led to the formation of cocrystals in which 2 and 3 share the crystal unit cell, held together through hydrogen bonding (Figure 1). The structure of 2 found in the cocrystal is consistent with the NMR data collected for the pure compound, which indicates a mer coordination of the PSiP ligand23 and an anti orientation of the hydride relative to the methyl at silicon. As a result of the monodentate coordination of the triflate, the complex remains five-coordinate: a feature difficult to ascertain in solution on the basis of NMR data.22 On the other hand, the cation of 3 is six-coordinate and features two weakly bonded water molecules, as inferred from the Ir(2)−O bond distances: 2.249(3) Å trans to hydride and 2.318(3) Å trans to silicon. The four hydrogen atoms of these water molecules, which were refined freely, are involved in hydrogen bonding with triflate oxygen atoms, with H···O distances in the range 1.96−2.19 Å. The cation also retains the mer coordination mode of the pincer as well as the anti orientation of the hydride.

The reversible reaction between 2 and water, leading to 3, confirms the higher robustness of the actual (PSiP)Ir skeleton compared to the aliphatic one and suggests that triflate displacement from 2 by conventional ligands (L) can easily lead to a variety of cationic compounds of the general formula [IrH{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}(L)2](CF3SO3). These are exemplified for L = NCMe (acetonitrile; 4) and CO (carbon monoxide; 5) in Scheme 1, which also illustrates an alternative preparation of these compounds from 1, silver triflate, and ligand excess. Complexes 4 and 5 were isolated as analytically pure solids and characterized by NMR as structurally analogous to 3. Complex 2 was also found to be capable of coordinating very weak ligands such as dihydrogen, although the product (6 in Scheme 2) proved too labile to be isolated as a solid. Scheme 2

As observed for water, dissolving dihydrogen in CD2Cl2 solutions of 2 at room temperature provoked shifts and broadenings of the NMR signals that reveal the reversible formation of new complexes in equilibrium with 2. Decoalescence of the broad resonances occurred below 260 K, rendering observable the hydride 1H NMR signals shown in Figure 2, which correspond to the major species at low temperature. The broad signal at δ −1.65 integrates twice as much as the triplet at δ −12.26 (JHP = 13.4 Hz) and displays a minimum T1 relaxation time of 7 ms, characteristic of a dihydrogen ligand.24 Within the range of temperature in which these 1H NMR signals are observable, the nOesy experiments 7191

DOI: 10.1021/acs.inorgchem.7b00833 Inorg. Chem. 2017, 56, 7190−7199

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Inorganic Chemistry

compatible with the estimations derived from the T1 min relaxation time.24 The chloride ligand of 1 can also be removed using sodium borohydride, to form the hydride−tetrahydroborate complex [IrH(κ2H-H2BH2){κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}] (7 in Scheme 3). Unlike the triflate derivative 2, complex 7 is sixScheme 3 Figure 2. 1H NMR hydride signals of complex 6 in CD2Cl2 at 233 K. The inset corresponds to the remaining signal observed after the treatment of 2 with dideuterium at this temperature.

do not evidence either their spatial proximity or the chemical exchange between them, thus suggesting a trans relative position of the hydride and dihydrogen ligands in the coordination sphere of the complex. The low-temperature NMR spectra also confirm triflate coordination to 6. Figure 3 compares the evolution with

coordinate as a result of the most common κ2H coordination of the tetrahydroborate ligand (Figure 4).27 As in the previous complexes, the pincer coordinates in the mer fashion and the terminal hydride occupies the face anti to the methyl at silicon. In agreement with the solid-state structure, the 1H NMR spectrum of 7 in C6D6 displays three signals in the hydride region: two broad resonances for the two nonequivalent bridges, at δ −3.91 and −7.11, and a triplet of doublets for the terminal hydride, at δ −17.89 (JHP = 15.5 Hz and JHH = 8.1 Hz, respectively). The latter JHH constant results from coupling to the bridging hydride in trans, H(1C) in the structure of Figure 4, as deduced from selective 1H NMR homodecoupling experiments and the 1H NMR nOesy spectrum (see the Supporting Information). This latter spectrum also evidences chemical exchange among the two equivalent terminal B−H hydrogen atoms, which share a broad signal at δ 7.60, and the bridging hydride H(1D). In contrast, neither the other bridging hydride H(1C) nor the Ir−H(1) terminal one join this or another chemical exchange below 350 K. This exchange scheme is what was expected for a facile release of the tetrahydroborate arm trans to silicon. As shown below, complex 7 constitutes a convenient entry into the chemistry of neutral and anionic polyhydrides. Yet, it can also afford cationic derivatives after treatment with Brønsted acids. In fact, its reaction with excess triflic acid in noncoordinating solvents quantitatively produced 2. In contrast, using HBF4 as a proton source stopped the reaction at an intermediate stage, affording the dinuclear cationic species [(μ:κ2H,κ2H-BH4)[IrH{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}]2](BF4) (8; Scheme 3). This complex readily precipitated from the reaction media when protonation was carried out in diethyl ether and was also observed to be the major product in the homogeneous reaction in dichloromethane, regardless of the equivalents of acid employed. Seemingly, in the absence of coordinating anions or solvents, expanding the tetrahydrobo-

Figure 3. Evolution with the temperature of the 19F NMR spectrum of (left) a solution of 2 and 0.4 equiv of water in CD2Cl2 and (right) the same solution under a H2 atmosphere (ca.1 bar).

temperature of 19F NMR spectra recorded for a sample of 2 with or without dissolved dihydrogen, in the presence of added water to reveal the chemical shift of the free triflate anion released after the formation of adduct 3. Clearly, the major product formed under dihydrogen shows a 19F chemical shift consistent with a coordinated triflate. Nevertheless, these and other spectra recorded for this equilibrium also suggest that the coordination behavior of dihydrogen is not limit to the formation of complex 6. In fact, the 19F NMR spectrum under dihydrogen at 193 K illustrates that the signal of 6 still broadens and shifts at low temperature, while the amount of free triflate increases, suggesting that triflate could eventually be released from 6 because of further dihydrogen coordination. Also, the coordination of dihydrogen in the position cis to hydride, expected to be kinetically favored in view of the structure of 2, is suggested by the fast deuteration of this ligand under dideuterium,25 unlikely to happen in the observable trans complex 6. Even though the H/D scrambling was found to be rapid (minutes) at low temperature, the 1H NMR spectra recorded at short reaction times allowed the observation of a residual signal for the η2-(HD) isotopomer of 6 featuring a JHD coupling constant of 31.5 ± 2 Hz (Figure 2). This value leads to a dihydrogen ligand H−H distance of 0.91 ± 0.04 Å,26 fully 7192

DOI: 10.1021/acs.inorgchem.7b00833 Inorg. Chem. 2017, 56, 7190−7199

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Inorganic Chemistry Scheme 4

competence of the mer-PSiP framework to define preferred coordination positions, even for incoming molecules as small as CO. A strong ν(CO) absorption at 1941 cm−1 in the IR spectrum of 9 confirms the presence of the carbonyl ligand, which also gives rise to a characteristic triplet at δ 181.82 (JCP = 5.7 Hz) in the 13C{1H} NMR spectrum. Two resonances in the 1 H NMR spectrum, at δ −13.95 and −10.97 in CDCl3, showing a mutual coupling constant of 3.4 Hz and displaying mutual NOE effects, confirm the cis relative position of the two hydride ligands. No chemical exchange among hydrides was detected in this case either. On the contrary, as previously reported,19 the tetrahydride 10 displays a single high-field resonance in the room temperature 1H NMR spectrum that corresponds to four rapidly exchanging hydride ligands. At low temperature (Figure 5), this average resonance decoalesces into two of relative integral 3:1, which feature a mutual JHH coupling constant of 6.2 Hz. The minimum T1 relaxation time of these hydride resonances is attained below decoalescence [400 MHz, tetrahydrofuran (THF)-d8], at about 220 K, and reaches a value of around 200 ms in both signals (see the Supporting

Figure 4. Structures of 7 (above left), the cation of 8 (below), and 9 (above right). Only one of the two independent molecules of 8 is represented. Ellipsoids for the anisotropic displacement parameters at the 50% level. Hydrogen atoms except hydrides have been omitted for the sake of clarity. For bond distances and angles, see the Supporting Information.

rate coordination mode to bridging is the only remaining option to offset the partial breakdown of this ligand, while protecting it from further protonation. Indeed, coordination to an additional cationic fragment is expected to reduce tetrahydroborate nucleophilicity, while the PSiP ligand substituents are likely to provide steric protection, as inferred from the X-ray structure of Figure 4. In agreement with the C2-symmetric structure found in the solid state, the solution 31P{1H} NMR of 8 shows a single AB pattern with a JPP coupling constant of 261.9 Hz: in the range expected for mutually trans phosphorus. In the 1H NMR spectrum, the bridging tetrahydroborate ligand features broad signals at δ −3.57 and −3.28. The two equivalent terminal hydrides display a ddd signal at δ −16.97, with two similar JHP coupling constants of about 17.3 Hz and just one observable JHH coupling of 4.5 Hz. No chemical exchange among hydrides was detected in this case. The reactions of 7 with alcohols led to either the dihydride− carbonyl derivative [IrH2{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}(CO)] (9) or the tetrahydride 10 (Scheme 4), depending on the ease of alcohol decarbonylation.28 Thus, primary alcohols such as methanol or ethanol quantitatively afforded 9, whereas 10 was the main product upon treatment with isopropyl alcohol. Complex 10 was also the product after the reaction of 7 with water in toluene. A closely related preparation of 10 and the X-ray structure of its analogue with tBu instead of iPr substituents have been previously reported.19 The carbonyl complex 9 was obtained as a single isomer, whose structure is that shown in Scheme 4 and Figure 4. This isomer was also that quantitatively formed after reaction of the tetrahydride 10 with excess CO. This evidences the

Figure 5. High-field region of the 1H NMR spectrum of the tetrahydride 10 in THF-d8 at different temperatures. The impurity at ca. δ −10.69 corresponds to a signal of complex 9. 7193

DOI: 10.1021/acs.inorgchem.7b00833 Inorg. Chem. 2017, 56, 7190−7199

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mer configuration with the P−Ir−P angle ranging from 155° (8 and 9) to 163° (1 and 2). The deviation from the exact trans angle 180° is always at the expense of the space available at the anti face versus Si−Me because the iridium atom is pushed out from the P−Si−P plane toward the syn face. Such a distortion is illustrated at the bottom of Figure 6 for the calculated structure of 10, which in this respect is similar to those of the low-energy dihydride−dihydrogen minima and the transition states TS1 and TS2. On the contrary, TS3 seems to require more space in the anti face and to this end brings the metal into the P−Si−P plane. This demands several minor bond elongations in the ligand skeleton that add up to give a significant barrier. In favor of such a steric rational, the analogue of 10 with tert-butyl instead of isopropyl groups at the pincer was reported to display the 3:1 pattern in the 1H NMR hydride region already at room temperature.19 Opposite to its distortion into a strictly mer ligand, this PSiP pincer can readily become fac-coordinating. The ease of such a transformation is illustrated by the behavior of the anionic trihydride [IrH3{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}]Na (11; Scheme 5), which was prepared from either 1 or 10 as an equilibrium mixture of mer and fac isomers.

Information). Although this discards the presence of direct H− H bonds and points to a classical tetrahydride structure, the intriguing 3:1 decoalescence pattern may conceivably suggest the involvement of some Si−H bonding interaction: a relatively common feature in the chemistry of PSiP pincers.29−32 Such a possibility was examined via a series of density functional theory calculations in THF, which proved to be inconclusive. Whereas PBE0 and wB97X-D optimized geometries of 10 are adequately described as iridium(V) tetrahydrides with the closest Si−H distances of 2.21 and 2.07 Å, respectively, the MN15-L optimized structure possesses a bridging hydride at 1.79 Å from silicon and 1.67 Å from the metal. Further calculations found two higher-energy minima corresponding to trans- and cis,syn-iridium(III) dihydrides: [IrH2(η2-H2){κP,P,SiSi(Me)(C6H4-2-PiPr2)2}] (Figure 6). The third possible

Scheme 5

Figure 6. (Top) MN15-L calculated free energy (ΔG, kcal mol−1) profile for hydride exchange in 10. (Bottom) View along the P···P axis of the structures calculated for 10 and the transition states.

The reaction was observed by NMR to be selective when starting from 10 and 1 equiv of NaH, or from 1 and NaH excess, although only in a THF-d8 solution. Subsequent manipulations aimed at the precipitation and isolation of the products always led to mixtures containing 10 and various unidentified complexes as impurities. Yet, the isomer fac-11 could be crystallized from a THF solution stored at low temperature and was characterized by X-ray diffraction (Figure 7). Its structure, featuring three hydride ligands in a facial arrangement, agrees with the hydride 1H NMR signals of the major isomer in solution, which correspond to the AMM′ part of an AMM′XX′ spin system (X = 31P). Simulation of these signals (Figure 8 above) requires cis and trans JHP coupling constants for each of the chemically equivalent hydrides (108.0 and 20.0 Hz, respectively) and a mutual JPP′ coupling of about 10.0 Hz between the magnetically nonequivalent phosphorus. The latter is consistent with the P−Ir−P angles found in the Xray structure, in the range of 105.12(4)−106.45(4)°. The solidstate structure also features contacts between the hydrides and the sodium cations, in the range of 2.3−2.6 Å away from the positions assigned to the hydrides, which are likely responsible for the actual dimeric assembly in the solid state. The cations complete their coordination sphere with a molecule of THF, which might account for the importance of this solvent in the reaction. Above 260 K, the NMR signals of 11 in THF-d8 are broadened because of the fast exchange between isomers. The position of the equilibrium also changes with the temperature, slightly favoring the mer isomer as the temperature decreases.

dihydrogen structure, with the H2 ligand anti to the methyl at silicon, could be optimized at the MN15-L level but was not found at the PBE0 level. The results of our calculations mostly resemble those obtained for the parent pincer tetrahydrides (PCP)IrH4 and (POCOP)IrH4, although obviously for these higher-symmetry complexes, the two cis-dihydride−dihydrogen minima are degenerate.33 The easy exchange among three of the hydrides of 10 could be readily modeled as facile dihydrogen ligand rotations in the dihydride−dihydrogen structures, as shown in Figure 6. In turn, the involvement of the fourth hydride in the exchange was found to be more energy-demanding, in agreement with the experimental observations. The calculated ΔH⧧ values for this latter exchange [13.5 (PBE0), 13.4 (mPW1k), and 14.2 (MN15-L) kcal mol−1] are reasonably close to ΔH⧧ = 12.4 ± 0.4 kcal mol−1 estimated from the experimental rates obtained via line-shape analysis of the 1H NMR hydride signals (see the Supporting Information for details). The free energy of the calculated dihydride−dihydrogen intermediate cis,anti-IrH2(H2) is 11.7 kcal mol−1 above 10 at the MN15-L level. This relatively high value and the hindered exchange of the corresponding hydrides in 10 should be attributed to spatial constraints. As appears from the X-ray structures of this work (none of which include sterically demanding equatorial ligands), the PSiP pincer ligand prefers a 7194

DOI: 10.1021/acs.inorgchem.7b00833 Inorg. Chem. 2017, 56, 7190−7199

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Inorganic Chemistry

The hydride region of the 1H NMR nOesy spectrum at 250 K shown in Figure 8 allows the assignment of three hydride signals of the isomer mer-11 via their mutual NOE effects (in red) and reveals the chemical exchanges among hydrides involved in the mer-to-fac isomerization (in blue, out of the diagonal). It is worth noting that the exchange cross-peaks twin the hydride ligands trans to silicon of each isomer (and, correspondingly, the other remaining four), while there are no intramolecular hydride ligand exchanges. Such an observation renders very unlikely any intramolecular isomerization mechanism and points to alternatives based on hydride ligand (H−) dissociations. The rates of isomerization, estimated between 282 and 313 K from the line width of the 31P{1H} NMR signal of fac-11, lead to the activation parameters ΔH⧧ = 12.0 ± 1.1 kcal mol−1 and ΔS⧧ = −11 ± 3 cal K−1 mol−1. The nonzero activation entropy also seems to discredit intramolecular mechanisms while again suggesting that cation and/ or solvent may play a role in the intermolecular hydride exchange.

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Figure 7. Structure of the fac isomer of complex 11. Only one of the two independent dimer molecules is represented. Ellipsoids for the anisotropic displacement parameters at the 50% level. Hydrogen atoms except hydrides have been omitted for the sake of clarity. For bond distances and angles, see the Supporting Information.

CONCLUDING REMARKS Chloride ligand replacement with triflate or tetrafluoroborate in the five-coordinate (PSiP)Ir precursor 1 gives access to a variety of hydride derivatives with different charges and different numbers of hydride ligands. Their structures and reactions confirm the relevance of the silyl group trans influence to define the coordination environments and the ability of this pincer in the mer coordination mode to discriminate between the two faces of its complexes. In fact, the dynamic behavior in solution observed for the tetrahydride 10 reveals that the spatial contour of the PSiP framework can condition phenomena as elusive as hydride ligand motions.

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EXPERIMENTAL SECTION

General Information. All manipulations were carried out with exclusion of air by using standard Schlenk techniques or in an argonfilled drybox (MBraun). Solvents were obtained from a solvent purification system (MBraun). Deuterated solvents were dried with appropriate drying agents and degassed with argon prior to use. Carbon, hydrogen, and nitrogen analyses were carried out in a PerkinElmer 2400 CHNS/O analyzer. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry were obtained in a Bruker Microflex mass spectrometer using 1,1-dicyano-4-tert-butylphenyl-3-methylbutadiene as a matrix. Attenuated-total-reflectance IR spectra of solid samples were run on a PerkinElmer Spectrum 100 FTIR spectrometer. NMR spectra were recorded on a Bruker Avance 400 or 300 MHz spectrometer. 1H (400.13 or 300.13 MHz) and 13C (100.6 or 75.5 MHz) NMR chemical shifts were measured relative to partially deuterated solvent peaks but are reported in parts per million relative to tetramethylsilane (TMS). 19F (376.5 MHz), 31P (162.0 or 121.5 MHz), 11B (96.3 MHz), and 29Si (79.5 or 59.6 MHz) chemical shifts were measured relative to CFCl3, H3PO4 (85%), BF3(OEt)2, and TMS, respectively. Coupling constants nJ and n,mN (=nJ + mJ′ for couplings with chemically equivalent but magnetically inequivalent nuclei) are given in hertz. In general, NMR spectral assignments were achieved through 1H{1H}, 1H cosy, 1H nOesy, 1H{31P}, 13C apt, and 1 H/13C hsqc experiments. Unless otherwise indicated, the NMR data are given at room temperature. The precursor complex 1 was prepared as previously described.19 All other reagents were commercial and were used as received. The new complexes described below are air-sensitive in solution and the solid state. Preparation of [IrH{κO-O3S(CF3)}{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}] (2). A solution of 1 (200 mg, 0.30 mmol) in CH2Cl2 (10 mL) was treated with methyl triflate (36 μL, 0.32 mmol) and stirred at room temperature for 24 h. Concentration of the resulting solution to ca. 0.5

Figure 8. High-field region of the 1H NMR nOesy spectrum of isomers 11 in THF-d8 at 250 K. Red cross-peaks denote signal enhancements (NOE), while blue ones correspond to the diagonal and signal detractions (saturation transfer). The calculated hydride region of the 1H NMR spectrum of fac-11 is shown on top.

Experimental equilibrium constants (K = [fac-11]/[mer-11]) were obtained from the integrals of the 31P{1H} NMR signals in the temperature range of 210−313 K, to estimate the equilibrium thermodynamic parameters as ΔH° = 1.3 ± 0.2 kcal mol−1 and ΔS° = 7.8 ± 0.7 cal K−1 mol−1. In line with what the structure of Figure 7 shows, the significant entropy change suggests a relevant role of the cation and/or the solvent in the stabilization of these anionic complexes, also in solution. 7195

DOI: 10.1021/acs.inorgchem.7b00833 Inorg. Chem. 2017, 56, 7190−7199

Article

Inorganic Chemistry

30.33 (vt, 1,3NCP = 35.6, PCHCH3), 130.42 (vt, 2,4NCP = 7.8, CH), 130.83 (vt, 4,5NCP = 8.8, CH), 132.65 (vt, 3,5NCP = 2.1, CH), 134.07 (vt, 3,4NCP = 19.1, CH), 138.43 (vt, 1,3NCP = 62.3, C), 153.17 (vt, 2,3 NCP = 37.0, C), 166.46 (t, 2JCP = 6.1, CO), 171.10 (t, 2JCP = 4.6, CO). 29Si{1H} NMR (CD2Cl2): δ 32.86 (t, 3JSiP = 2.1). [IrH{κO-O3S(CF3)}{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}(η2-H2)] (6). A solution of 2 (12.0 mg, 0.015 mmol) in 0.5 mL of CD2Cl2 contained in a poly(tetrafluoroethylene)-valved NMR tube was frozen. Then, the argon inside the tube was evacuated, and the tube was filled with hydrogen (1 bar) and sealed. At 233 K, the resulting mixture was observed by NMR to contain 2 together with a new complex 6, in a relative proportion of 3:5. Partial data for 6. 1H NMR (CD2Cl2, 233 K): δ −12.26 (t, 2JHP = 13.4, 1H, IrH), −1.65 (br, 2H, Ir(H2)), 0.24 (s, 3H, SiCH3), 7.36, 7.45, 7.69 (all m, 2H each, CH), 7.96 (d, 3JHH = 7.1, 2H, CH). 19F NMR (CD2Cl2, 233 K): δ −77.37 (s). 31P{1H} (CD2Cl2, 233 K): δ 59.23 (s). 29Si{1H} NMR (CD2Cl2, 233 K): δ 12.06 (s). Preparation of [IrH(κ2H-H2BH2){κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}] (7). A solution of 1 (296 mg, 0.45 mmol) and NaBH4 (88.7 mg, 2.25 mmol) in 10 mL of THF was stirred under reflux for 4 h. The solution was filtered through Celite, dried in vacuo, redissolved in toluene, and filtered again. The resulting solution was concentrated to ca. 0.5 mL and treated with hexane to obtain a pale-yellow solid. The solid was separated by decantation, washed with hexane, and dried in vacuo. Yield: 275 mg (96%). Anal. Calcd for C25H44BP2SiIr: C, 47.09; H, 6.96. Found: C, 46.65; H, 7.00. 1H NMR (C6D6): δ −17.89 (dt, 2JHP = 15.5, 2JHH = 8.1, 1H, IrH), −7.11, −3.91 (both br, 1H each, IrH2BH2), 0.70 (dvt, 3JHH = 8.0, 3,5NHP = 15.0, 6H, PCHCH3), 0.84 (s, 3H, SiCH3), 1.02 (dvt, 3JHH = 7.2, 3,5NHP = 14.6, 6H, PCHCH3), 1.06 (dvt, 3 JHH = 7.8, 3,5NHP = 17.0, 6H, PCHCH3), 1.27 (dvt, 3JHH = 8.5, 3,5NHP = 15.5, 6H, PCHCH3), 2.41, 277 (both m, 2H each, PCHCH3), 7.09, 7.22 (both dd, 3JHH = 3JHH′ ≈ 7.3, 2H each, CH), 7.34 (m, 2H, CH), 7.60 (br, 2H, IrH2BH2), 8.08 (d, 3JHH = 7.3, 2H, CH). 31P{1H} NMR (C6D6): δ 60.98 (s). 11B{1H} NMR (C6D6): δ 10.95 (brs), 13C{1H} NMR (C6D6): δ 6.89 (s, SiCH3), 16.46 (vt, 2,4NCP = 2.8, PCHCH3), 17.59 (vt, 2,4NCP = 4.8, PCHCH3), 20.12 (vt, 2,4NCP = 4.5, PCHCH3), 20.42 (vt, 2,4NCP = 3.4, PCHCH3), 24.03 (vt, 1,3NCP = 25.3, PCHCH3), 24.11 (vt, 1,3NCP = 32.7, PCHCH3), 127.19 (vt, 3,5NCP = 7.2, CH), 129.64 (s, CH), 130.24 (vt, 2,4NCP = 5.5, CH), 132.65 (vt, 3,4NCP = 18.8, CH), 142.72 (vt, 1,3NCP = 54.3, C), 159.32 (vt, 2,4NCP = 42.0, C), 29 Si{1H} NMR (C6D6): δ 26.45 (t, 3JSiP = 2.9). The crystals used in the X-ray diffraction experiment were obtained from a hexane solution stored at 253 K. Preparation of [(μ:κ 2 H,κ 2 H-BH 4 )[IrH{κP,P,Si-Si(Me)(C 6 H 4 -2PiPr2)2}]2](BF4) (8). A commercial solution of tetrafluoroboric acid in diethyl ether (54%, 19 μL, 0.14 mmol) was added dropwise to a solution of 7 (174 mg, 0.27 mmol) in 10 mL of CH2Cl2. The mixture was stirred for 2 h, concentrated to ca. 0.5 mL, and treated with dry diethyl ether to obtain a pale-yellow solid. The solid was separated by decantation, washed with diethyl ether, and dried in vacuo. Yield: 87.0 mg (47%). The microanalysis data and NMR spectra of the bulk samples indicate the presence of various minor impurities, which could not be removed by recrystallization. Anal. Calcd for C50H84B2F4P4Si2Ir2: C, 44.57; H, 6.28. Found: C, 44.09; H, 5.83. 1H NMR (CDCl3): δ −16.97 (dd, 2JHP ≈ 17.3, 2JHH = 4.5, 2H, IrH), −3.57, −3.28 (both vbr, 2H each, H2BH2), 0.73 (s, 6H, SiCH3), 0.76, 0.83 (both m, 3JHH ≈ 6.7, 6H each, PCHCH3), 0.92, 0.96 (both m, 3 JHH ≈ 7.1, 6H each, PCHCH3), 1.23, 1.27, 1.29, 1.35 (all m, 3JHH ≈ 6.7, 6H each, PCHCH3), 2.54, 2.62, 2.81, 2.89 (all m, 2H each, PCHCH3), 7.43, 7.52, 7.60 (all m, 4H each, CH), 8.11 (d, 3JHH ≈ 7.4, 4H, CH). 19F NMR (CD2Cl2): δ −152.82 (br). 31P{1H} NMR (CD2Cl2): δ 57.57 (AB spin system δA = 59.70, δB = 55.43, 2JAB = 261.9). 11B{1H} NMR (CD2Cl2): δ −1.21 (s, BF4), 17.19 (br, BH4). 13 C{1H} NMR (CDCl3): δ 7.41 (s, SiCH3), 17.10 (d, 2JCP = 3.6, PCHCH3), 17.25 (d, 2JCP = 3.2, PCHCH3), 19.47, 19.63 (both dd, 2JCP ≈ 3.6, 4JCP = 1.6, PCHCH3), 19.95, 20.10 (both s, PCHCH3), 20.33, 21.43 (both d, 2JCP ≈ 1.7, PCHCH3), 24.96, 25.09 (both dd, 1JCP ≈ 24.8, 3JCP ≈ 12.3, PCHCH3), 26.47, 26.99 (both dd, 1JCP ≈ 16.8, 3JCP ≈ 8.4, PCHCH3), 128.77, 129.73 (both m, CH), 130.74 (s, CH),

mL and the addition of hexane (3 mL) produced a pale-yellow solid, which was separated by decantation and dried in vacuo. Yield: 181 mg (78%). Anal. Calcd for C26H40F3O3P2SSiIr: C, 40.46; H, 5.22. Found: C, 40.83; H, 5.24. 1H NMR (CD2Cl2): δ −29.52 (t, 2JHP = 14.9, 1H, IrH), 0.56 (s, 3H, SiCH3), 0.95 (dvt, 3JHH = 8.7, 3,5NHP = 15.8, 6H, PCHCH3), 1.06 (dvt, 3JHH = 10.3, 3,5NHP = 16.2, 6H, PCHCH3), 1.30 (dvt, 3JHH = 5.6, 3,5NHP = 12.4, 6H, PCHCH3), 1.42 (dvt, 3JHH = 9.8, 3,5 NHP = 15.6, 6H, PCHCH3), 2.90, 3.20 (both m, 2H each, PCHCH3), 7.38, 7.46 (both dd, 3JHH = 3JHH′ ≈ 7.3, 2H each, CH), 7.58 (m, 2H, CH), 8.06 (d, 3JHH = 7.3, 2H, CH). 19F NMR (CD2Cl2): δ −77.49 (s). 31P{1H} NMR (CD2Cl2): δ 69.60 (s). 13C{1H} NMR (CD2Cl2): δ 2.63 (s, SiCH3), 17.99 (vt, 2,4NCP = 3.2, PCHCH3), 18.91 (vt, 2,4NCP = 6.4, PCHCH3), 19.73 (vt, 2,4NCP = 4.4, PCHCH3), 20.53 (vt, 2,4NCP = 2.3, PCHCH3), 26.05 (vt, 1,3NCP = 24.6, PCHCH3), 26.30 (vt, 1,3NCP = 31.8, PCHCH3), 120.84 (q, 1JCF = 319.3, SO3CF3), 128.42 (vt, 3,5NCP = 7.2, CH), 130.23 (s, CH), 131.25 (vt, 2,4NCP = 5.3, CH), 131.85 (vt, 3,4NCP = 17.8, CH), 140.16 (vt, 1,3NCP = 53.8, C), 155.56 (vt, 2,3NCP = 40.3, C), 29Si{1H} NMR (CD2Cl2): δ 8.94 (s). [IrH{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}(OH2)2](CF3SO3) (3). A solution of 2 (12.0 mg, 0.015 mmol) in 0.5 mL of CD2Cl2 was treated with 1 μL of water. The NMR at 173 K spectra revealed a mixture of 2 and a new complex, 3, in a relative proportion of 1:6. Partial data for 3. 1H NMR (CD2Cl2, 173 K): δ −28.86 (brt, 2JHP ≈ 16.0, 1H, IrH), 0.32 (s, 3H, SiCH3), 0.75, 1.16 (both br, 12H each, PCHCH3), 2.69, 3.11 (both br, 2H each, PCHCH3), 4.30, 4.89 (both br, 2H each, IrOH2), 7.30, 7.39, 7.50 (all m, 2H each, CH), 8.02 (d, 3JHH = 7.0, 2H, CH). 19 F NMR (CD2Cl2, 233 K): δ −78.98 (s). 31P{1H} (CD2Cl2, 233 K): δ 54.46 (s). Preparation of [IrH{κP,P,Si-Si(Me)(C 6 H 4 -2-PiPr 2 ) 2 }(NCMe) 2 ](SO3CF3) (4). A solution of 1 (200 mg, 0.30 mmol) in acetone/ acetonitrile (5/1 mL) was treated with silver triflate (77.1 mg, 0.30 mmol) and stirred for 24 h in the dark. The resulting suspension was filtered through Celite to remove the insoluble silver chloride and concentrated to ca. 0.5 mL. The addition of diethyl ether (3 mL) produced a pale-yellow solid, which was separated by decantation, washed with diethyl ether, and dried in vacuo. Yield: 172 mg (67%). Anal. Calcd for C36H46F3N2O3P2SSiIr: C, 42.20; H, 5.43; N, 3.28. Found: C, 41.90; H, 5.02; N, 3.48. 1H NMR (CDCl3): δ −21.35 (t, 2 JHP = 16.5, 1H, IrH), 0.33 (s, 3H, SiCH3), 1.04 (dvt, 3JHH = 7.5, 3,5 NHP = 14.7, 6H, PCHCH3), 1.09 (dvt, 3JHH = 7.3, 3,5NHP = 14.3, 6H, PCHCH3), 1.21 (m, 12H, PCHCH3), 2.46 (brs, 3H, NCCH3), 2.51 (s, 3H, NCCH3), 2.80 (m, 4H, PCHCH3), 7.33, 7.43 (both dd, 3JHH = 3 JHH′ ≈ 7.3, 2H each, CH), 7.58 (m, 2H, CH), 8.04 (d, 3JHH = 7.3, 2H, CH). 19F NMR (CDCl3): δ −78.13 (s). 31P{1H} NMR (CDCl3): δ 48.30 (s). 13C{1H} NMR (CDCl3): δ 3.30, 3.59 (both s, NCCH3), 3.88 (s, SiCH3), 18.40 (s, PCHCH3), 18.47 (vt, 2,4NCP = 2.3, PCHCH3), 18.63 (vt, 2,4NCP = 3.9, PCHCH3), 19.45 (s, PCHCH3), 26.87 (vt, 1,3NCP = 32.0, PCHCH3), 27.68 (vt, 1,3NCP = 25.1, PCHCH3), 123.20 (brs, NCCH3), 128.15 (vt, 3,5NCP = 7.5, CH), 129.43 (vt, 2,4NCP = 5.9, CH), 129.98 (s, CH), 132.38 (vt, 3,4NCP = 18.8, CH), 141.69 (vt, 1,3NCP = 57.2, C), 156.44 (vt, 2,3NCP = 41.3, C), 29 Si{1H} NMR (CDCl3): δ 19.87 (t, 3JSiP = 3.9). Preparation of [IrH{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}(CO)2](SO3CF3) (5). Carbon monoxide was slowly bubbled for 1 min through a solution of 2 (123 mg, 0.16 mmol) in CH2Cl2 (10 mL). The resulting solution was taken to dryness, and the residue was treated with diethyl ether to give a white solid. The solid was separated by decantation, washed with diethyl ether, and dried in vacuo. Yield: 119 mg (90%). IR (cm−1): 2140 [ν(IrH)], 2079 [ν(CO)], 2028 [ν(CO)], 1258 [ν(SO3)]. Anal. Calcd for C28H40F3O5P2SSiIr: C, 40.62; H, 4.87. Found: C, 41.02; H, 5.32. 1H NMR (CD2Cl2): δ −11.66 (t, 2JHP = 15.0, 1H, IrH), 0.75 (s, 3H, SiCH3), 1.03, 1.10 (both dvt, 3JHH = 6.9, 3,5 NHP = 17.1, 6H each, PCHCH3), 1.24, 1.29 (both m, 3JHH = 6.9, 3,5 NHP ≈ 15.4, 6H each, PCHCH3), 2.79, 2.95 (both m, 2H each, PCHCH3), 7.58, 7.67 (both dd, 3JHH = 3JHH′ ≈ 7.2, 2H each, CH), 7.74 (m, 2H, CH), 8.16 (d, 3JHH = 7.2, 2H, CH). 19F NMR (CDCl3): δ −78.13 (s). 31P{1H} NMR (CD2Cl2): δ 56.18 (s). 13C{1H} NMR (CD2Cl2): δ 3.55 (s, SiCH3), 18.61, 18.80, 19.77 (all s, PCHCH3), 19.79 (vt, 2,4NCP = 2.9, PCHCH3), 30.10 (vt, 1,3NCP = 29.2, PCHCH3), 7196

DOI: 10.1021/acs.inorgchem.7b00833 Inorg. Chem. 2017, 56, 7190−7199

Article

Inorganic Chemistry 132.39, 132.57 (both dd, 3JCP ≈ 4.7, 5JCP ≈ 2.4, CH), 140.09, 141.30 (both d, 1JCP ≈ 43.4, C), 154.22, 154.39 (both dd, 2JCP ≈ 28.4, 4JCP ≈ 5.9, C). 29Si{1H} NMR (CD2Cl2): δ 31.15 (brs). The crystals used in the X-ray diffraction experiment were obtained from a THF solution stored at 253 K. Preparation of [IrH2{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}(CO)] (9). A solution of 7 (200 mg, 0.30 mmol) in toluene/methanol (10/1 mL) was stirred under reflux for 1 h. The resulting solution was filtered, evaporated to dryness, cooled to 213 K, and treated with hexane (3 mL) to obtain a white solid. The solid was separated by decantation, washed with hexane, and dried in vacuo. Yield: 153 mg (78%). Anal. Calcd for C26H41OP2SiIr: C, 47.91; H, 6.34. Found: C, 47.90; H, 6.32. IR (cm−1): 2090 ν(IrH), 1941 ν(CO). 1H NMR (CDCl3): δ −13.95 (td, 2JHP = 19.1, 2JHH = 3.4, 1H, IrH), −10.97 (td, 2JHP = 14.5, 2JHH = 3.4, 1H, IrH), 0.62 (dvt, 3JHH = 7.9, 3,5NHP = 15.2, 6H, PCHCH3), 0.68 (s, 3H, SiCH3), 1.07 (m, 12H, PCHCH3), 1.27 (dvt, 3JHH = 8.1, 3,5NHP = 15.6, 6H, PCHCH3), 2.35, 2.45 (both m, 2H each, PCHCH3), 7.25, 7.38 (both dd, 3JHH = 3JHH′ ≈ 7.3, 2H each, CH), 7.48 (m, 2H, CH), 8.13 (d, 3JHH = 7.3, 2H, CH). 31P{1H} NMR (CDCl3): δ 62.93 (s). 13 C{1H} NMR (CDCl3): δ 5.83 (s, SiCH3), 17.63 (s, PCHCH3), 18.89 (vt, 2,4NCP = 4.5, PCHCH3), 19.62 (s, PCHCH3), 20.00 (vt, 2,4NCP = 3.7, PCHCH3), 24.27 (vt, 1,3NCP = 37.4, PCHCH3), 30.17 (vt, 1,3NCP = 27.5, PCHCH3), 127.17 (vt, 3,5NCP = 7.6, CH), 129.03 (vt, 2,4NCP = 6.4, CH), 129.41 (s, CH), 132.76 (vt, 3,4NCP = 18.5, CH), 144.96 (vt, 1,3 NCP = 57.2, C), 159.96 (vt, 2,3NCP = 40.0, C), 181.82 (t, 2JCP = 5.7, CO). 29Si{1H} NMR (C6D6): δ 34.87 (t, 3JSiP = 5.9). The crystals used in the X-ray diffraction experiment were obtained from a CDCl3 solution stored at 253 K. Preparation of [IrH4{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}] (10). A suspension of 7 (255 mg, 0.40 mmol) in 15 mL of isopropyl alcohol was stirred under reflux for 4 h. The resulting dark-orange solution was evaporated to dryness, and the residue was dissolved in toluene and filtered through Celite. The solution was then concentrated to ca. 0.5 mL and treated with hexane (3 mL) to obtain a white solid. The solid was separated by decantation, washed with hexane, and dried in vacuo. Yield: 185 mg (74%). The spectroscopic data obtained for the solid dissolved in C6D6 match those previously published for complex 10 in ref 17. [IrH3{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}]Na (11). A solution of 1 (33.0 mg, 0.05 mmol) in THF-d8 (0.5 mL) was treated with NaH (8.0 mg, 0.32 mmol) and stored at 280 K. Periodic NMR monitoring of the reaction indicated the complete disappearance of the starting material after 5 days at this temperature. The low-temperature NMR spectra indicated the selective formation of two new compounds in an approximate molar ratio of 9:1, which correspond to isomers fac-11 and mer-11, respectively. Data for fac-11. 1H NMR (250 K, THF-d8): δ −14.92 (m, 2JHP = 108.0, 20.0, 2JHH = 6.5, 2H, IrH), −12.38 (tt, 2JHP = 12.8, 2JHH = 6.5, 1H, IrH), 0.55 (dd, 3JHP = 12.2, 3JHH = 6.8, 6H, PCHCH3), 0.61 (s, 3H, SiCH3), 0.65 (dd, 3JHP = 13.4, 3JHH = 6.7, 6H, PCHCH3), 1.10 (dd, 3JHP = 13.0, 3JHH = 6.5, 12H, PCHCH3), 1.89, 2.03 (both m, 2H each, PCHCH3), 6.97, 7.07 ((both dd, 3JHH = 3JHH′ ≈ 7.3, 2H each, CH), 7.43 (dd, 3JHH ≈ 7.3, 3JHP = 4.1, 2H, CH), 7.83 (d, 3JHH ≈ 7.3, 2H, CH). 31P{1H} NMR (250 K, THF-d8): δ 57.41 (s). 13 C{1H} NMR (250 K, THF-d8): δ 5.16 (t, 3JCP = 3.4, SiCH3), 19.88 (s, PCHCH3), 20.23 (t, JCP = 2.5, PCHCH3), 21.58 (t, JCP = 3.7, PCHCH3), 22.79 (s, PCHCH3), 27.20, 28.00 (both m, PCHCH3), 125.88 (t, 3,5JCP = 2.2, CH), 127.96 (s, CH), 128.26 (t, 2,4JCP = 1.2, CH), 132.47 (m, CH), 151.59 (m, C), 164.48 (m, C). 29Si{1H} NMR (250 K, THF-d8): δ 35.51 (t, 3JSiP = 8.1). Data for mer-11. 1 H NMR (250 K, THF-d8): δ −16.25 (tdd, 2JHP ≈ 19.4, 2JHH = 2JHH′ = 4.2, 1H, IrH), −14.92 (tdd, 2JHP ≈ 11.3, 2JHH = 2JHH′ = 4.2, 1H, IrH), −13.34 (tdd, 2JHP ≈ 14.6, 2JHH = 2JHH′ = 4.2, 1H, IrH), 0.50 (s, 3H, SiCH3), 0.62 (m, 6H, PCHCH3), 1.04 (m, 12H, PCHCH3), 1.16 (dvt, 3JHH = 6.8, 3,5NHP = 14.3, 6H, PCHCH3), 1.80, 2.31 (both m, 2H each, PCHCH3), 7.01, 7.12 (both dd, 3JHH = 3JHH′ ≈ 7.2, 2H each, CH), 7.40 (m, 2H, CH), 8.05 (d, 3JHH ≈ 7.2, 2H, CH). 31P{1H} NMR (250 K, THF-d8): δ 68.17 (s). 13C{1H} NMR (250 K, THF-d8): δ 8.98 (t, 3 JCP = 0.9, SiCH3), 17.62 (s, PCHCH3), 19.77 (vt, 2,4NCP = 9.0, PCHCH3), 20.97 (vt, 2,4NCP = 3.3, PCHCH3), 21.93 (vt, 2,4NCP = 5.1,

PCHCH3), 23.11 (vt, 1,3NCP = 33.5, PCHCH3), 32.49 (vt, 1,3NCP = 24.0, PCHCH3), 125.56 (vt, 3,5NCP = 5.4, CH), 127.88 (s, CH), 128.94 (vt, 2,4NCP = 3.5, CH), 132.43 (m, CH), 149.90 (vt, 1,3NCP = 53.2, C), 165.34 (vt, 2,4NCP = 45.7, C). 29Si{1H} NMR (250 K, THF-d8): δ 40.36 (t, 3JSiP = 11.2). The crystals used in the X-ray diffraction experiment were obtained from a THF solution stored at 253 K. Computational Details. The PBE1PBE (also known as PBE0)34 and mPW1k35 calculations were carried out in Gaussian 09 (revision A2) using tight optimizations and the ultrafine integration grid [a pruned (99,590) grid]. The basis sets included 6-31+G(3pd) for the hydrides, Def2QZVPP (with the corresponding ECP) for the iridium atom, 6-311+G(d) for phosphorus and silicon atoms, and 631+G(d,p) for all other atoms. The default polarizble continuum method (solvent = THF) was used in all Gaussian 09 calculations with the UFF radii scaled by 1.1 (explicit hydrogen atoms). The MN15-L36 calculations of this work were carried out in Gaussian 1637 using Def2QZVP (with def2 ECP) for the iridium atom and the Def2TZVP basis set for all other atoms together with the W06 density fitting basis set.38,39 The polarizable continuum model (IEFPCM) was used in the Gaussian 16 calculations in a THF solvent, with the radii and nonelectrostatic terms of Truhlar and co-workers’ SMD solvation model (scrf = smd).40 All optimized geometries were verified to have the correct number of negative harmonic frequencies by frequency calculations, which also provided the reported enthalpies and free energies at 298.15 K. Structural Analysis of Complexes 1, 2 + 3, 7−9, and 11. X-ray data were collected at 100.0(2) K on Bruker Smart APEX CCD (1, 7, 8, and 11) and Smart APEX CCD DUO (2 + 3 and 9) diffractometers using graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). Single crystals were mounted on a fiber and covered with protective perfluoropolyether. Data were collected over the complete sphere by a combination of four sets (1, 2 + 3, 7, and 9) or three sets (8 and 11). Each frame exposure time was 20 s (1, 7, and 11), 30 s (3 + 2), 10 s (9), or 5 s (8), covering 0.3° in ω. Data were corrected for absorption by using a multiscan method applied with the SADABS program.41 The structures were solved by the Patterson method and refined by full-matrix least squares on F2 using the Bruker SHELXTL program package,42 including isotropic and subsequently anisotropic displacement parameters for all non-hydrogen nondisordered atoms. Weighted R factors (Rw) and goodness of fit (GOF; S) are based on F2, and conventional R factors are based on F. Data for 1: C25H40ClP2SiIr, mol wt 658.27; yellow irregular block, 0.20 × 0.04 × 0.04 mm3; monoclinic, space group C2/c; a = 32.1770(18) Å, b = 11.5057(7) Å, c = 15.3676(9) Å; β = 99.8800(10)°; Z = 8; V = 5605.0(6) Å3; Dcalc = 1.560 g cm−3; μ = 5.027 mm−1, minimum and maximum transmission factors 0.500 and 0.710; 2θmax = 57.60; 32669 reflections collected, 6864 unique [R(int) = 0.0334]; number of data/restraints/parameters 6864/0/284; final GOF 0.973, R1 = 0.0233 [5845 reflections I > 2σ(I)], wR2 = 0.0582 for all data; largest peak and hole +2.826 (close to the iridium atoms) and −0.611 e Å−3. Hydrogen atoms (except the hydride) were calculated using a restricted riding model on their respective carbon atoms with the thermal parameter related to the bonded atom. The hydride was refined freely. Data for 2 + 3: C26H40F3O3P2SSiIr·C25H44O2P2SiIr·CF3SO3, mol wt 1579.81; yellow irregular block, 0.10 × 0.08 × 0.06 mm3; triclinic, space group P1;̅ a = 12.3098(9) Å, b = 15.0326(11) Å, c = 18.0143(13) Å; α = 70.0400(10)°, β = 86.9170(10)°, γ = 85.6840(10)°; Z = 2; V = 3123.0(4) Å3; Dcalc = 1.680 g cm−3; μ = 4.530 mm−1, minimum and maximum transmission factors 0.831 and 1.000; 2θmax = 59.14; 33075 reflections collected, 15865 unique [R(int) = 0.0347]; number of data/restraints/parameters 15865/2/ 727; final GOF 0.871, R1 = 0.0290 [11870 reflections I > 2σ(I)], wR2 = 0.0538 for all data; largest peak and hole +1.852 (close to the iridium atoms) and −1.027 e Å−3. Hydrogen atoms of both water ligands were observed in the difference Fourier maps and refined freely. Hydride ligands were observed in the difference Fourier maps and refined by fixing the Ir−H bond lengths to 1.59(1) Å, the average value found in the Cambridge Structural Database. The rest of the 7197

DOI: 10.1021/acs.inorgchem.7b00833 Inorg. Chem. 2017, 56, 7190−7199

Article

Inorganic Chemistry hydrogen atoms were calculated and refined using a restricted riding model on their respective carbon atoms. Data for 7: C25H44BP2SiIr, mol wt 637.66; colorless irregular block, 0.32 × 0.18 × 0.18 mm3; triclinic, space group P1̅; a = 11.7034(7) Å, b = 14.9572(9) Å, c = 16.5817(10) Å; α = 104.1290(10)°, β = 95.3820(10)°, γ = 92.0490(10)°; Z = 4; V = 2797.2(3) Å3; Dcalc = 1.514 g cm−3; μ = 4.941 mm−1, minimum and maximum transmission factors 0.254 and 0.455; 2θmax = 57.60; 34963 reflections collected, 13216 unique [R(int) = 0.0294]; number of data/restraints/ parameters 13216/0/599; final GOF 0.965, R1 = 0.0218 [11911 reflections I > 2σ(I)], wR2 = 0.0564 for all data; largest peak and hole +2.087 (close to the iridium atoms) and −0.970 e Å−3. Hydrogen atoms (except hydrides) were calculated using a restricted riding model on their respective carbon atoms with the thermal parameter related to the bonded atom. Hydrides were refined freely. Data for 8: C50H84BP4Si2Ir2BF4·2.7C4H8O, mol wt 1528.26; colorless irregular block, 0.22 × 0.14 × 0.08 mm3; triclinic, space group P1̅; a = 15.0151(15) Å, b = 16.3668(17) Å, c = 16.8562(17) Å; α = 95.1790(10)°, β = 110.5820(10)°, γ = 102.7900(10)°; Z = 2; V = 3717.1(7) Å3; Dcalc = 1.358 g cm−3; μ = 3.740 mm−1, minimum and maximum transmission factors 0.502 and 0.672; 2θmax = 56.38; 34340 reflections collected, 16892 unique [R(int) = 0.0571]; number of data/restraints/parameters 16892/171/781; final GOF 0.934, R1 = 0.0564 [9765 reflections I > 2σ(I)], wR2 = 0.1498 for all data; largest peak and hole +3.168 and −2.007 e Å−3. Hydride ligands were observed in the difference Fourier maps and refined with fixed thermal parameters and positional restraints. The rest of the hydrogen atoms were calculated and refined using a restricted riding model on their respective carbon atoms. Four crystallization molecules of THF were observed in the unit cell and refined with restraints in the geometry and thermal parameters. The highest electronic residuals were observed in the proximity of these THF molecules. Data for 9: C26H42OP2SiIr, mol wt 651.84; colorless irregular block, 0.20 × 0.06 × 0.04 mm3; monoclinic, space group P21/n; a = 8.9090(8) Å, b = 21.3533(19) Å, c = 14.9136(13) Å; β = 105.0290(10)°; Z = 4; V = 2740.1(4) Å3; Dcalc = 1.580 g cm−3; μ = 5.049 mm−1, minimum and maximum transmission factors 0.494 and 0.678; 2θmax = 59.10; 28307 reflections collected, 7181 unique [R(int) = 0.0367]; number of data/restraints/parameters 7181/0/297; final GOF 0.891, R1 = 0.0220 [5966 reflections I > 2σ(I)], wR2 = 0.0457 for all data; largest peak and hole +1.594 (close to the iridium atoms) and −0.946 e Å−3. Hydrogen atoms (except hydrides) were calculated using a restricted riding model on their respective carbon atoms with the thermal parameter related to the bonded atom. Hydrides were refined freely. Data for 11: C25H42P2SiIr·Na·C4H8O, mol wt 719.93; colorless irregular block, 0.36 × 0.18 × 0.14 mm3; monoclinic, space group P21/c; a = 31.0378(15) Å, b = 21.1623(10) Å, c = 20.2672(10) Å; β = 107.3840(10)°; Z = 16; V = 12704.1(11) Å3; Dcalc = 1.506 g cm−3; μ = 4.376 mm−1, minimum and maximum transmission factors 0.373 and 0.495; 2θmax = 57.48; 116321 reflections collected, 30225 unique [R(int) = 0.0410]; number of data/restraints/parameters 30225/12/ 1334; final GOF 1.004, R1 = 0.0360 [22761 reflections I > 2σ(I)], wR2 = 0.0750 for all data; largest peak and hole +2.570 (close to the iridium atoms) and −1.758 e Å−3. Hydride ligands were observed in the difference Fourier maps but not refined properly. Because of that, all Ir−H bond lengths were fixed to the same value, 1.59(1) Å, the average value found in the Cambridge Structural Database, and restraints were applied to the hydride’s thermal parameters. The rest of the hydrogen atoms were calculated and refined using a restricted riding model on their respective carbon atoms. A crystallization molecule of THF was observed in the unit cell and refined freely.

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NMR spectra of complexes 2−11, details of the NMR kinetic and thermodynamic determinations, and energies of the calculated compounds and transitions states (PDF) Calculated complex coordinates (XYZ) Accession Codes

CCDC 1549479−1549484 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (E.S.). *E-mail: [email protected] (M.M.). ORCID

Eduardo Sola: 0000-0001-5462-6189 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS Financial support from the Spanish MINECO [Grants CTQ2012-31774 and BES2013-063359 (to E.S.) and CTQ2015-64486-R], Gobierno de Aragón (E75), FEDER, and the European Social Fund is acknowledged.

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REFERENCES

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b00833. 7198

DOI: 10.1021/acs.inorgchem.7b00833 Inorg. Chem. 2017, 56, 7190−7199

Article

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